Wolter Prins

Production and characterization of slow pyrolysis biochar: influence of feedstock type and pyrolysis conditions

Biochar was produced by fixed‐bed slow pyrolysis from various feedstock biomasses under a range of process conditions. Feedstocks used were pine wood, wheat straw, green waste and dried algae. Process conditions varied were the highest treatment temperature (HTT) and residence time. The produced chars were characterized by proximate analysis, CHN‐elemental analysis, pH in solution, bomb calorimetry for higher heating value, N2 adsorption for BET surface area and two biological degradation assays (oxygen demand, carbon mineralization in soil). In proximate analysis, it was found that the fixed carbon content (expressed in wt% of dry and ash‐free biochar) in the biochar samples strongly depended on the intensity of the thermal treatment (i.e. higher temperatures and longer residence times in the pyrolysis process). The actual yield in fixed carbon (i.e. the biochar fixed carbon content expressed as wt% of the dry and ash‐free original feedstock biomass weight) was practically insensitive to the highest treatment temperature or residence time. The pH in solution, higher heating value and BET surface positively correlated with pyrolysis temperature. Finally, soil incubation tests showed that the addition of biochar to the soil initially marginally reduced the C‐mineralization rate compared against the control soil samples, for which a possible explanation could be that the soil microbial community needs to adapt to the new conditions. This effect was more pronounced when adding chars with high fixed carbon content (resulting from more severe thermal treatment), as chars with low fixed carbon content (produced through mild thermal treatment) had a larger amount of volatile, more easily biodegradable, carbon compounds.

Quantitative analysis of crude and stabilized bio-oils by comprehensive two-dimensional gas-chromatography.

Bio-oils produced by fast pyrolysis of lignocellulosic biomass have proven to be a promising, clean, and renewable energy source. To better assess the potential of using bio-oils for the production of chemicals and fuels a new comprehensive characterization method is developed. The combination of the analyical power of GC×GC-FID and GC×GC-TOF-MS allows to obtain an unseen level of detail for both crude and hydrotreated bio-oils originated from pine wood biomass. The use of GC×GC proves to be essential to capture the compositional differences between crude and stabilized bio-oils. Our method uses a flame ionization detector to quantify the composition, while GC×GC-TOF-MS is used for the qualitative analysis. This method allows quantification of around 150 tentatively identified compounds, describing approximately 80% of total peak volume. The number of quantified compounds in bio-oils is increased with a factor five compared to the present state-of-the-arte. The necessity of using multiple internal standards (dibutyl ether and fluoranthene) and a cold-on column injector is also verified.

Influence of strain-specific parameters on hydrothermal liquefaction of microalgae.

Algae are an interesting feedstock for producing biofuel via hydrothermal liquefaction (HTL), due to their high water content. In this study, algae slurries (5-7 wt% daf) from different species were liquefied at 250 and 375 °C in batch autoclaves during 5 min. The aim was to analyze the influence of strain-specific parameters (cell structure, biochemical composition and growth environment) on the HTL process. Results show big variations in the biocrude oil yield within species at 250 °C (from 17.6 to 44.8 wt%). At 375 °C, these differences become less significant (from 45.6 to 58.1 wt%). An appropriate characterization of feedstock appeared to be critical to interpret the results. If a high conversion of microalgae-to-biocrude is pursued, near critical conditions are required, with Scenedesmus almeriensis (freshwater) and Nannochloropsis gaditana (marine) leading to the biocrude oils with lower nitrogen content from each growth environment.

Assessing microalgae biorefinery routes for the production of biofuels via hydrothermal liquefaction

The interest in third generation biofuels from microalgae has been rising during the past years. Meanwhile, it seems not economically feasible to grow algae just for biofuels. Co-products with a higher value should be produced by extracting a particular algae fraction to improve the economics of an algae biorefinery. The present study aims at analyzing the influence of two main microalgae components (lipids and proteins) on the composition and quantity of biocrude oil obtained via hydrothermal liquefaction of two strains (Nannochloropsis gaditana and Scenedesmus almeriensis). The algae were liquefied as raw biomass, after extracting lipids and after extracting proteins in microautoclave experiments at different temperatures (300-375°C) for 5 and 15min. The results indicate that extracting the proteins from the microalgae prior to HTL may be interesting to improve the economics of the process while at the same time reducing the nitrogen content of the biocrude oil.

Cost‐benefit analysis of using biochar to improve cereals agriculture

Biochar has received considerable scientific attention in the past decade as a possible method for carbon storage and increasing agricultural yields. Despite this promise, however, economic assessments of biochar are yet to definitively establish the value of the technology, primarily due to discrepancy between observed short‐term agronomic benefits and expectations of biochar as a lasting soil improver. This study investigated the economic value of biochar as an agricultural technology for long‐term improvement of arable farming. From presently available field trial data, the costs and benefits of using biochar technology to enhance cereals agriculture were evaluated in two generalized geo‐economic agricultural scenarios: North‐Western Europe (NWE) and Sub‐Saharan Africa (SSA). Cost models were developed to estimate the total cost of biochar from initial biomass feedstock acquisition to final soil application for each agricultural setting. Benefits of biochar application were estimated by statistical meta‐analysis of crop yield data from published biochar field trials to find the increase in cereal grain yield attributable to biochar application for both NWE (+0.07 to +0.28 t ha−1 yr−1) and SSA (+0.18 to +1.00 t ha−1 yr−1). The grain yield improvement from a one‐time biochar application was assumed to persist without decay for an independently varying time period, and the increase in grain production then monetised using projected future commodity prices. The Net Present Value (NPV) of applying biochar was then calculated by setting present total costs against present total benefits as a function of biochar performance longevity. Biochar application was found to carry a positive NPV for cereal cropping in SSA in several scenarios where the duration of the biochar yield effect was assumed to extend 30 years into the future. Conversely, NWE biochar scenarios were all found to have negative NPVs even when the benefits time span was indefinitely stretched.

Potential of genetically engineered hybrid poplar for pyrolytic production of bio-based phenolic compounds.

Wild-type and two genetically engineered hybrid poplar lines were pyrolyzed in a micro-pyrolysis (Py-GC/MS) and a bench scale setup for fast and intermediate pyrolysis studies. Principal component analysis showed that the pyrolysis vapors obtained by micro-pyrolysis from wood of caffeic acid O-methyltransferase (COMT) and caffeoyl-CoA O-methyltransferase (CCoAOMT) down-regulated poplar trees differed significantly from the pyrolysis vapors obtained from non-transgenic control trees. Both fast micro-pyrolysis and intermediate pyrolysis of transgenic hybrid poplars showed that down-regulation of COMT can enhance the relative yield of guaiacyl lignin-derived products, while the relative yield of syringyl lignin-derived products was up to a factor 3 lower. This study indicates that lignin engineering via genetic modifications of genes involved in the phenylpropanoid and monolignol biosynthetic pathways can help to steer the pyrolytic production of guaiacyl and syringyl lignin-derived phenolic compounds such as guaiacol, 4-methylguaiacol, 4-ethylguaiacol, 4-vinylguaiacol, syringol, 4-vinylsyringol, and syringaldehyde present in the bio-oil.

Mild hydrothermal conditioning prior to torrefaction and slow pyrolysis of low-value biomass

The aim of this research was to establish whether hydrothermal conditioning and subsequent thermochemical processing via batch torrefaction or slow pyrolysis may improve the fuel quality of grass residues. A comparison in terms of fuel quality was made of the direct thermochemical processing of the feedstock versus hydrothermal conditioning as a pretreatment prior to thermochemical processing. Hydrothermal conditioning reduced ash content, and particularly nitrogen, potassium and chlorine contents in the biomass. The removal of volatile organic matter associated with thermochemical processes can increase the HHV to levels of volatile bituminous coal. However, slow pyrolysis only increased the HHV of biomass provided a low ash content (<6%) feedstock was used. In conclusion, hydrothermal conditioning can have a highly positive influence on the efficiency of thermochemical processes for upgrading low-value (high-ash) biomass to a higher quality fuel.

Cleaning of Hot Producer Gas in a Catalytic Adiabatic Packed Bed Reactor with Periodic Flow Reversal

To use the product gas of a biomass gasification unit in, for instance, gas engines, its tar content must be reduced to less then 100 mg/Nm3 [1]. A novel technology has been tested which is characterised by periodic reversal of the gas flow through a packed-bed tar removal reactor. Because the entrance and outlet sections of the reactor act as efficient heat exchangers, the producer gas leaves the reactor at relatively low temperatures. A small fraction of the producer gas is burned in situ to supply the energy required for the tar conversion reactions. This way of operation provides a high degree of heat integration.

Carbonization of biomass

Carbonization is a slow pyrolysis process in which biomass is converted into a highly carbonaceous, charcoal-like material. Typically, carbonization consists of heating the biomass in an oxygen-free or oxygen-limited environment, and reaction conditions are tailored to maximize the production of char. Traditionally, charcoal production is one of the oldest chemical conversion processes known to mankind. Even today, charcoal production continues on a large scale worldwide, and is still making use—in part—of tradition charcoal kilns. Furthermore, there is renewed interest to carbonization, both from a scientific and a commercial point of view, for the production and application of biochar and torrefied biomass. This chapter gives an overview of carbonization, its chemistry, and the physicochemical properties of the resulting products. It also highlights the effects of feedstock properties and process conditions and concludes with an overview of traditional and modern carbonization techniques.

Sub- and supercritical water oxidation of anaerobic fermentation sludge for carbon and nitrogen recovery in a regenerative life support system

Sub- and supercritical water oxidation was applied to recover carbon as CO2, while maintaining nitrogen as NH4+ or NO3-, from sludge obtained from an anaerobic fermenter running on a model waste composed of plant residues and human fecal matter. The objective was to fully convert carbon in the organic waste to CO2 while maintaining nutrients (specifically N) in the liquid effluent. In regenerative life support systems, CO2 and nutrients could then be further used in plant production; thus creating a closed carbon and nutrient cycle. The effect of the operational parameters in water oxidation on carbon recovery (C-to-CO2) and nitrogen conversion (to NH4+, NO3-) was investigated. A batch micro-autoclave reactor was used, at pressures ranging between 110 and 300 bar and at temperatures of 300-500 °C using hydrogen peroxide as oxidizer. Residence times of 1, 5 and 10 min were tested. Oxidation efficiency increased as temperature increased, with marginal improvements beyond the critical temperature of water. Prolonging the residence time improved only slightly the carbon oxidation efficiency. Adequate oxygen supply, i.e., exceeding the stoichiometrically required amount, resulted in high carbon conversion efficiencies (>85%) and an odorless, clear liquid effluent. However, the corresponding oxidizer use efficiency was low, up to 50.2% of the supplied oxygen was recovered as O2 in the effluent gas and did not take part in the oxidation. Volatile fatty acids (VFAs) were found as the major soluble organic compounds remaining in the effluent liquid. Nitrogen recovery was high at 1 min residence time (>94.5%) and decreased for longer residence times (down to 36.4% at 10 min). Nitrogen in the liquid effluent was mostly in the form of ammonium.